JP2013199683A - Method for producing metal thallium - Google Patents
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- JP2013199683A JP2013199683A JP2012068757A JP2012068757A JP2013199683A JP 2013199683 A JP2013199683 A JP 2013199683A JP 2012068757 A JP2012068757 A JP 2012068757A JP 2012068757 A JP2012068757 A JP 2012068757A JP 2013199683 A JP2013199683 A JP 2013199683A
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- thallium
- sulfuric acid
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- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 147
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000002244 precipitate Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000000571 coke Substances 0.000 claims abstract description 11
- -1 thallium halide Chemical class 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 113
- 238000002386 leaching Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000779 smoke Substances 0.000 claims description 23
- 229910052794 bromium Inorganic materials 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 16
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 2
- 239000011133 lead Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 26
- 238000000926 separation method Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000011085 pressure filtration Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000011135 tin Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000003929 acidic solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
本発明は、タリウム含有溶液から高純度の金属タリウムを製造する方法に関する。 The present invention relates to a method for producing high-purity metallic thallium from a thallium-containing solution.
タリウムは、鉛製造原料に微量に含まれていることが多い。そのため、鉛の製錬工程においては、タリウムは不純物であり、除去が望まれている。また、タリウムの除去が進まないと鉛製錬の工程内で循環して濃縮され、製品鉛中のタリウム品位が徐々に上昇することになる。このため、鉛製錬工程から金属タリウムの回収及び分離が望まれている。一方、タリウム（Ｔｌ）は有価金属であり、産業上さまざまな分野で使用されており、産業上の利用の点から、金属タリウムの回収、及び金属タリウムの製造方法の提供が望まれている。 Thallium is often contained in trace amounts in the lead production raw material. Therefore, thallium is an impurity in the lead smelting process, and its removal is desired. Moreover, if thallium removal does not proceed, it will be circulated and concentrated in the lead smelting process, and the thallium quality in the product lead will gradually rise. For this reason, recovery and separation of metal thallium are desired from the lead smelting process. On the other hand, thallium (Tl) is a valuable metal and is used in various industrial fields. From the viewpoint of industrial use, recovery of metal thallium and provision of a method for producing metal thallium are desired.
このため、例えば、鉛電気炉煙灰からタリウムを分離し、金属タリウムとして回収する方法がある（特許文献１参照）。この金属タリウムの回収方法について図１に示す。まず、鉛電気炉煙灰に水を加えて撹拌し、硫酸及び酸化剤を添加することで、タリウムは水に溶け、鉛は硫酸鉛として沈殿するので、ろ過によって分離することができる。次に、ろ液に塩化源及び還元剤を加えるとタリウムは塩化タリウム（ＴｌＣｌ）として沈殿する。これを洗浄してカドミニウムを除去後、２００℃の濃硫酸に溶かすと、Ｃｌ（塩素）を除去できる。得られたタリウム溶液をｐＨ調整・硫化剤添加により残ったカドミニウムや鉛を除去後、亜鉛板を用いてセメンテーション反応を行うと、ほぼタリウム金属のスポンジタリウムが得られる。これにＮａＯＨフラックスを添加して溶融するとタリウム金属が得られる。 For this reason, for example, there is a method of separating thallium from lead electric furnace smoke ash and recovering it as metal thallium (see Patent Document 1). This metal thallium recovery method is shown in FIG. First, water is added to the lead electric furnace ash and stirred, and sulfuric acid and an oxidant are added, so that thallium dissolves in water and lead precipitates as lead sulfate and can be separated by filtration. Next, when a chloride source and a reducing agent are added to the filtrate, thallium precipitates as thallium chloride (TlCl). This is washed to remove cadmium and then dissolved in concentrated sulfuric acid at 200 ° C. to remove Cl (chlorine). When the obtained thallium solution is subjected to a cementation reaction using a zinc plate after removing residual cadmium and lead by adjusting the pH and adding a sulfurizing agent, a thallium metal sponge thallium is obtained. When a NaOH flux is added to this and melted, thallium metal is obtained.
しかし、前記提案の方法では、還元工程で塩化源を添加しており、Ｃｌ（塩素）を除去するため、２００℃の濃硫酸を用いており、高温の酸に対応した装置、条件設定が必要であり、装置の長大化、設備費用の重装備化が必要である。また、セメンテーション反応は、反応速度が遅く、この方法では５時間反応させる必要があり、長時間を要する。
このため、鉛電気炉煙灰からのタリウムの分離が従来のように塩化源を添加することなく適用できることが望まれていた。
また、鉛電気炉煙灰には、臭素（Ｂｒ）が含まれており、このような臭素を含む鉛電気炉煙灰の有効利用が望まれていた。
However, in the proposed method, a chlorination source is added in the reduction step, and concentrated sulfuric acid at 200 ° C. is used to remove Cl (chlorine), so it is necessary to set up equipment and conditions corresponding to high-temperature acid. Therefore, it is necessary to lengthen the equipment and make heavy equipment costs. Further, the cementation reaction has a slow reaction rate, and in this method, it is necessary to react for 5 hours, which takes a long time.
For this reason, it has been desired that separation of thallium from lead electric furnace ash can be applied without adding a chlorination source as in the prior art.
Further, bromine (Br) is contained in the lead electric furnace smoke ash, and effective utilization of such lead electric furnace smoke ash containing bromine has been desired.
したがって、従来のように高温の酸性溶液を使用することなく、簡易な方法で、更に短時間で高純度の金属タリウムを効率よく製造できる方法の提供が望まれていた。 Therefore, it has been desired to provide a method capable of efficiently producing high-purity metal thallium in a shorter time without using a hot acidic solution as in the prior art.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、高温の酸性溶液を使用せずに、簡易な方法で、短時間で高純度の金属タリウムを効率よく製造する金属タリウムの製造方法を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a method for producing metal thallium that can efficiently produce high-purity metal thallium in a short time without using a high-temperature acidic solution.
前記課題を解決するため、従来のような湿式反応とは全く異なる乾式反応にも着目し本発明者が鋭意検討を重ねた結果、タリウム含有溶液に還元剤を加えてタリウム沈殿物とし、前記タリウム沈殿物にアルカリ塩及び還元源を加えて溶融することにより、従来のような高温の２００℃の濃硫酸を用いる必要がなく、セメンテーション反応よりも短い時間で高純度の金属タリウムを効率よく製造できることを知見した。 In order to solve the above-mentioned problems, the present inventor has intensively studied paying attention to a dry reaction completely different from the conventional wet reaction, and as a result, the thallium precipitate is obtained by adding a reducing agent to the thallium-containing solution. By adding an alkali salt and a reducing source to the precipitate and melting it, there is no need to use high-temperature 200 ° C concentrated sulfuric acid as in the past, and high-quality metallic thallium is efficiently produced in a shorter time than the cementation reaction. I learned that I can do it.
本発明は、本発明者による前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ タリウム含有溶液に還元剤を加えてタリウム沈殿物とし、前記タリウム沈殿物にアルカリ塩及び還元源を加えて溶融することを特徴とする金属タリウムの製造方法である。
＜２＞ タリウム含有溶液が、鉛電気炉煙灰に水、硫酸及び酸化剤の少なくともいずれかを加えて浸出した液である前記＜１＞に記載の金属タリウムの製造方法である。
＜３＞ タリウム沈殿物が臭化タリウム及び塩化タリウムのいずれかであり、
アルカリ塩がＮａＯＨ及びＫＯＨのいずれかであり、
還元源がコークスである前記＜１＞から＜２＞のいずれかに記載の金属タリウムの製造方法である。
＜４＞ タリウム及び臭素を含む鉛電気炉煙灰に、水及び硫酸の少なくともいずれかを加えてスラリーとし、該スラリーを硫酸浸出液と硫酸残渣とに固液分離する硫酸浸出工程と、
前記硫酸残渣に水、硫酸及び酸化剤の少なくともいずれかを加えてスラリーとし、該スラリーを酸化浸出液と残渣とに固液分離する酸化浸出工程と、
を含む前記＜１＞から＜３＞のいずれかに記載の金属タリウムの製造方法である。
＜５＞ ハロゲン化タリウムにアルカリ塩及び還元源を加えて溶融することを特徴とする金属タリウムの製造方法である。
＜６＞ ハロゲン化タリウムが、臭化タリウム及び塩化タリウムのいずれかであり、
還元源がコークスである前記＜５＞に記載の金属タリウムの製造方法である。
＜７＞ 溶融が７００℃以上の温度で行われる前記＜１＞から＜６＞のいずれかに記載の金属タリウムの製造方法である。
This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1> A method for producing metallic thallium, characterized in that a reducing agent is added to a thallium-containing solution to form a thallium precipitate, and an alkali salt and a reducing source are added to the thallium precipitate and melted.
<2> The method for producing metal thallium according to <1>, wherein the thallium-containing solution is a liquid leached by adding at least one of water, sulfuric acid, and an oxidizing agent to lead electric furnace smoke ash.
<3> The thallium precipitate is either thallium bromide or thallium chloride,
The alkali salt is either NaOH or KOH;
The method for producing metal thallium according to any one of <1> to <2>, wherein the reduction source is coke.
<4> A sulfuric acid leaching step in which at least one of water and sulfuric acid is added to a lead electric furnace smoke ash containing thallium and bromine to form a slurry, and the slurry is solid-liquid separated into a sulfuric acid leaching solution and a sulfuric acid residue,
Adding at least one of water, sulfuric acid, and an oxidizing agent to the sulfuric acid residue to form a slurry, and oxidizing and leaching the solid to separate the slurry into an oxidative leachate and a residue;
The method for producing metal thallium according to any one of <1> to <3>, including:
<5> A method for producing metal thallium, characterized in that an alkali salt and a reducing source are added to thallium halide and melted.
<6> The thallium halide is either thallium bromide or thallium chloride,
It is a manufacturing method of the metal thallium as described in said <5> whose reduction source is coke.
<7> The method for producing metal thallium according to any one of <1> to <6>, wherein melting is performed at a temperature of 700 ° C. or higher.
本発明においては、タリウム含有溶液に還元剤を加えてタリウム沈殿物とし、前記タリウム沈殿物にアルカリ塩及び還元源を加えて溶融することにより、従来のような高温の濃硫酸を用いる必要がなく、セメンテーション反応よりも短い時間で効率よく高純度の金属タリウムを製造することができる。
また、硫酸浸出工程においてＦｅ（２価）等を予め分離することで、酸化浸出工程における酸化剤の必要量を低減することができる。
In the present invention, a thallium-containing solution is added with a reducing agent to form a thallium precipitate, and an alkali salt and a reducing source are added to the thallium precipitate and melted, thereby eliminating the need for conventional high-temperature concentrated sulfuric acid. High-purity metal thallium can be efficiently produced in a shorter time than the cementation reaction.
Further, by separating Fe (divalent) and the like in advance in the sulfuric acid leaching step, the required amount of oxidant in the oxidative leaching step can be reduced.
本発明によると、従来における前記諸問題を解決することができ、高温の酸性溶液を使用せずに、簡易な方法で、短時間で高純度の金属タリウムを効率よく製造する金属タリウムの製造方法を提供することができる。 According to the present invention, a method for producing metal thallium that can solve the above conventional problems and efficiently produces high-purity metal thallium in a short time without using a high-temperature acidic solution. Can be provided.
（金属タリウムの製造方法）
本発明の金属タリウムの製造方法は、タリウム含有溶液に還元剤を加えてタリウム沈殿物とし、前記タリウム沈殿物にアルカリ塩及び還元源を加えて溶融することを特徴とする。
(Metallic thallium production method)
The method for producing metal thallium according to the present invention is characterized in that a reducing agent is added to a thallium-containing solution to form a thallium precipitate, and an alkali salt and a reducing source are added to the thallium precipitate and melted.
前記金属タリウムの製造方法は、酸化浸出工程と、還元工程と、還元溶融工程とを含み、硫酸浸出工程、更に必要に応じてその他の工程を含んでなる。
本発明において、前記硫酸浸出工程は、必須の工程ではなく、必要に応じて含むことができるが、前記酸化浸出工程の前に、前記硫酸浸出工程を行うことで、工程数は増えるが、前記酸化浸出工程における酸化剤の使用量を低減することができ、前記硫酸浸出工程を行わない場合に比べて多量にタリウム沈殿物が得られる点で有利である。
The method for producing metal thallium includes an oxidation leaching step, a reduction step, and a reduction melting step, and further includes a sulfuric acid leaching step and, if necessary, other steps.
In the present invention, the sulfuric acid leaching step is not an indispensable step, and can be included as necessary, but by performing the sulfuric acid leaching step before the oxidation leaching step, the number of steps increases, The amount of the oxidizing agent used in the oxidative leaching step can be reduced, which is advantageous in that a large amount of thallium precipitate can be obtained as compared with the case where the sulfuric acid leaching step is not performed.
＜硫酸浸出工程＞
前記硫酸浸出工程は、鉛電気炉煙灰に、水及び硫酸の少なくともいずれかを加えてスラリーとし、該スラリーを硫酸浸出液と硫酸浸出残渣とに固液分離する工程である。
<Sulfuric acid leaching process>
The sulfuric acid leaching step is a step in which at least one of water and sulfuric acid is added to lead electric furnace smoke ash to form a slurry, and the slurry is solid-liquid separated into a sulfuric acid leaching solution and a sulfuric acid leaching residue.
＜＜鉛電気炉煙灰＞＞
前記鉛電気炉煙灰は、鉛製錬の電気炉において発生した煙灰であり、鉛製錬の他、銅製錬等の非鉄製錬における乾式工程にて発生する煙灰であってタリウムが含まれていれば適用可能である。なお、非鉄製錬以外からの原料としては、タリウムが他の元素と混合されているもの、タリウム含有物、排水でもよい。更には、タリウムと臭素が含まれている溶液、含有物であってもよい。
前記鉛電気炉煙灰には、タリウムの他、臭素、鉛、錫、鉄、カドミウム、亜鉛、銅、ヒ素、アンチモンが含まれている。
前記鉛電気炉煙灰に臭素が一定量以上含まれていると、後の還元工程においてタリウム含有溶液に臭素又は塩素を添加する必要はないか、あるいは添加量を少なくすることができる。
<< Lead electric furnace smoke ash >>
The lead electric furnace smoke ash is smoke ash generated in a lead smelting electric furnace, and in addition to lead smelting, it is smoke ash generated in a dry process in non-ferrous smelting such as copper smelting and contains thallium. If applicable. In addition, as raw materials other than non-ferrous smelting, thallium mixed with other elements, thallium-containing materials, and waste water may be used. Further, it may be a solution containing thallium and bromine.
The lead electric furnace ash contains bromine, lead, tin, iron, cadmium, zinc, copper, arsenic, and antimony in addition to thallium.
When a certain amount or more of bromine is contained in the lead electric furnace smoke ash, it is not necessary to add bromine or chlorine to the thallium-containing solution in the subsequent reduction step, or the addition amount can be reduced.
前記硫酸浸出工程では、まず、前記鉛電気炉煙灰に水をスラリー濃度４５０ｇ／Ｌ以下になるように加える。前記スラリー濃度は、高いほど処理効率が良好なので、スラリー濃度１００ｇ／Ｌ〜４００ｇ／Ｌが好ましい。
前記水としては、液媒体であれば特に制限はなく、目的に応じて適宜選択することができる。
硫酸を加えて室温（２５℃）以上で１時間以上撹拌し、固液分離する。撹拌速度は、直径９０ｍｍの撹拌羽を用いた場合には、３００ｒｐｍ以上である。前記撹拌時間は１時間〜２時間が好ましい。前記撹拌羽の形状としては、特に制限はなく、目的に応じて適宜選択することができ、２段タービン羽などが挙げられる。
前記固液分離としては、特に制限はなく、目的に応じて適宜選択することができるが、加圧ろ過が好ましい。
前記硫酸浸出工程により、タリウム以外の不純物元素、例えば、Ｆｅ（鉄）、Ｃｄ（カドミニウム）、Ｚｎ（亜鉛）、Ｃｕ（銅）等がろ液として硫酸浸出液に分離される。一方、Ｐｂ（鉛）、Ｓｎ（錫）、Ｔｌ（タリウム）等が残渣として硫酸浸出残渣に残る。また、臭素の８５質量％〜９０質量％も硫酸浸出液に分離される。なお、前記硫酸浸出工程においては、硫酸の濃度は、特に制限はなく、目的に応じて適宜選択することができ、硫酸を添加しなくてもよいが、ｐＨ０．５〜１．５の範囲であることが好ましい。
In the sulfuric acid leaching step, first, water is added to the lead electric furnace ash so that the slurry concentration is 450 g / L or less. Since the higher the slurry concentration, the better the processing efficiency, the slurry concentration is preferably 100 g / L to 400 g / L.
There is no restriction | limiting in particular as said water if it is a liquid medium, According to the objective, it can select suitably.
Sulfuric acid is added, and the mixture is stirred at room temperature (25 ° C.) or more for 1 hour or more, and solid-liquid separation is performed. The stirring speed is 300 rpm or more when a stirring blade having a diameter of 90 mm is used. The stirring time is preferably 1 hour to 2 hours. There is no restriction | limiting in particular as a shape of the said stirring blade, According to the objective, it can select suitably, A two-stage turbine blade etc. are mentioned.
There is no restriction | limiting in particular as said solid-liquid separation, Although it can select suitably according to the objective, Pressure filtration is preferable.
By the sulfuric acid leaching step, impurity elements other than thallium, for example, Fe (iron), Cd (cadmium), Zn (zinc), Cu (copper) and the like are separated into the sulfuric acid leaching solution as a filtrate. On the other hand, Pb (lead), Sn (tin), Tl (thallium), etc. remain as residues in the sulfuric acid leaching residue. In addition, 85% to 90% by mass of bromine is also separated into the sulfuric acid leachate. In the sulfuric acid leaching step, the concentration of sulfuric acid is not particularly limited and can be appropriately selected according to the purpose, and it is not necessary to add sulfuric acid, but in the range of pH 0.5 to 1.5. Preferably there is.
＜酸化浸出工程＞
前記酸化浸出工程は、前記硫酸浸出残渣又は前記鉛電気炉煙灰に、水、硫酸及び酸化剤の少なくともいずれかを加えてスラリーとし、該スラリーを酸化浸出液と残渣とに固液分離する工程である。
前記酸化浸出工程により、タリウムは固液分離によってろ液である酸化浸出液に分離される。前記酸化浸出液中のタリウム以外の不純物元素としては、例えば、鉛、錫、ヒ素、臭素などが挙げられる。
<Oxidation leaching process>
The oxidation leaching step is a step of adding at least one of water, sulfuric acid, and an oxidizing agent to the sulfuric acid leaching residue or the lead electric furnace smoke ash to form a slurry, and solid-liquid-separating the slurry into an oxidation leaching solution and a residue. .
Through the oxidative leaching step, thallium is separated into an oxidative leachate which is a filtrate by solid-liquid separation. Examples of impurity elements other than thallium in the oxidative leach solution include lead, tin, arsenic, and bromine.
前記酸化浸出工程では、まず、前記硫酸浸出工程で得られた硫酸浸出残渣に水をスラリー濃度６００ｇ／Ｌ以下になるように加えて撹拌する。
前記スラリー濃度は、高いほど処理効率が良好なので、スラリー濃度２００ｇ／Ｌ〜６００ｇ／Ｌが好ましい。
前記水としては、液媒体であれば特に制限はなく、目的に応じて適宜選択することができる。
前記スラリーは、硫酸を添加することにより、ｐＨを０．３以下に調整することが好ましく、ｐＨ０〜０．３に調整することがより好ましい。
前記硫酸の濃度は、上記ｐＨ範囲であれば特に制限はなく、目的に応じて適宜選択することができる。
In the oxidation leaching step, first, water is added to the sulfuric acid leaching residue obtained in the sulfuric acid leaching step so as to have a slurry concentration of 600 g / L or less and stirred.
Since the higher the slurry concentration, the better the processing efficiency, the slurry concentration is preferably 200 g / L to 600 g / L.
There is no restriction | limiting in particular as said water if it is a liquid medium, According to the objective, it can select suitably.
The slurry is preferably adjusted to a pH of 0.3 or less by adding sulfuric acid, and more preferably to a pH of 0 to 0.3.
There is no restriction | limiting in particular if the density | concentration of the said sulfuric acid is the said pH range, According to the objective, it can select suitably.
前記酸化剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、過マンガン酸カリウム、過硫酸ソーダなどが挙げられる。
前記酸化剤の添加量は、タリウムに対して、１．５倍当量〜３倍当量が好ましく、２倍当量〜２．５倍当量がより好ましい。
前記酸化剤を添加して室温（２５℃）以上で１時間以上撹拌し、固液分離する。前記撹拌時間としては１時間〜２時間が好ましい。撹拌速度は、直径９０ｍｍの撹拌羽を用いた場合には、３００ｒｐｍ以上が好ましい。前記撹拌羽の形状としては、特に制限はなく、目的に応じて適宜選択することができ、２段タービン羽などが挙げられる。
前記固液分離としては、特に制限はなく、目的に応じて適宜選択することができるが、加圧ろ過が好ましい。
前記酸化浸出工程、又は前記硫酸浸出工程及び前記酸化浸出工程を行うことにより、鉛電気炉煙灰から酸化浸出液としてのタリウム含有溶液が得られる。
There is no restriction | limiting in particular as said oxidizing agent, According to the objective, it can select suitably, For example, potassium permanganate, sodium persulfate, etc. are mentioned.
The addition amount of the oxidizing agent is preferably 1.5 times equivalent to 3 times equivalent to thallium, and more preferably 2 times equivalent to 2.5 times equivalent.
The oxidizing agent is added, and the mixture is stirred at room temperature (25 ° C.) or more for 1 hour or more, and solid-liquid separation is performed. The stirring time is preferably 1 to 2 hours. The stirring speed is preferably 300 rpm or more when a stirring blade having a diameter of 90 mm is used. There is no restriction | limiting in particular as a shape of the said stirring blade, According to the objective, it can select suitably, A two-stage turbine blade etc. are mentioned.
There is no restriction | limiting in particular as said solid-liquid separation, Although it can select suitably according to the objective, Pressure filtration is preferable.
By performing the oxidation leaching step, or the sulfuric acid leaching step and the oxidation leaching step, a thallium-containing solution as an oxidative leachate is obtained from the lead electric furnace smoke ash.
＜＜タリウム含有溶液＞＞
前記タリウム含有溶液としては、タリウムを含有していれば特に制限はなく、目的に応じて適宜選択することができるが、鉛電気炉煙灰に、水、硫酸、及び酸化剤の少なくともいずれかを加えて、浸出した液であることが好ましく、前記硫酸浸出工程及び前記酸化浸出工程を行って得られた酸化浸出液がより好ましい。
前記タリウム含有溶液中には、タリウム以外の不純物元素として、例えば、鉛、錫、ヒ素、臭素などを含んでいる。
<< Thallium-containing solution >>
The thallium-containing solution is not particularly limited as long as it contains thallium and can be appropriately selected according to the purpose. However, at least one of water, sulfuric acid, and an oxidizing agent is added to the lead electric furnace smoke ash. The leached liquid is preferably a leached liquid, and the oxidized leached liquid obtained by performing the sulfuric acid leaching step and the oxidative leaching step is more preferable.
The thallium-containing solution contains, for example, lead, tin, arsenic, bromine and the like as impurity elements other than thallium.
＜還元工程＞
前記還元工程は、前記タリウム含有溶液に還元剤を加えてタリウム沈殿物を得る工程である。
<Reduction process>
The reduction step is a step of adding a reducing agent to the thallium-containing solution to obtain a thallium precipitate.
前記タリウム含有溶液中に臭素が含まれていない場合には、前記タリウム含有溶液に臭素及び塩素のいずれかを添加する。前記タリウム含有溶液に臭素及び塩素のいずれかを添加すればよく、前記タリウム含有溶液中に臭素が１．５当量以上含まれている場合には、臭素及び塩素のいずれかを添加しなくてよい。
前記還元剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、亜硫酸ソーダ、亜硫酸ガスなどが挙げられる。前記還元剤は不純物になり得る元素を含まないものを用いることが好ましい。
前記還元剤の添加量は、タリウムに対して、０．４倍当量〜０．５倍当量が好ましく、０．３倍当量〜０．５倍当量がより好ましい。
撹拌羽の形状としては、特に制限はなく、目的に応じて適宜選択することができ、２段タービン羽などが挙げられる。
撹拌速度は、直径９０ｍｍの撹拌羽を用いた場合、２００ｒｐｍ以上が好ましい。
撹拌時間は、特に制限はなく、目的に応じて適宜選択することができるが、１時間〜２時間が好ましい。
この際、ＴｌＢｒ（臭化タリウム）が沈殿し、タリウム沈殿物（ＴｌＢｒ沈殿物）が発生するので、ろ過等の固液分離により回収する。
When bromine is not contained in the thallium-containing solution, either bromine or chlorine is added to the thallium-containing solution. Either bromine or chlorine may be added to the thallium-containing solution, and when bromine is contained in an amount of 1.5 equivalents or more in the thallium-containing solution, either bromine or chlorine may not be added. .
There is no restriction | limiting in particular as said reducing agent, According to the objective, it can select suitably, For example, sodium sulfite, sulfurous acid gas, etc. are mentioned. It is preferable to use a reducing agent that does not contain an element that can be an impurity.
The addition amount of the reducing agent is preferably 0.4 times equivalent to 0.5 times equivalent to thallium, and more preferably 0.3 times equivalent to 0.5 times equivalent.
There is no restriction | limiting in particular as a shape of a stirring blade, According to the objective, it can select suitably, A two-stage turbine blade etc. are mentioned.
The stirring speed is preferably 200 rpm or more when a stirring blade having a diameter of 90 mm is used.
There is no restriction | limiting in particular in stirring time, Although it can select suitably according to the objective, 1 hour-2 hours are preferable.
At this time, TlBr (thallium bromide) precipitates and thallium precipitates (TlBr precipitates) are generated, which are collected by solid-liquid separation such as filtration.
＜還元溶融工程＞
前記還元溶融工程は、前記タリウム沈殿物にアルカリ塩及び還元源を加えて溶融する工程である。前記アルカリ塩及び前記還元源を加える順番はいずれかの順でもよいが、タリウム沈殿物にアルカリ塩及び還元源が同一容器内に設置されてから加熱し、溶融するのが好ましい。
<Reduction melting process>
The reducing and melting step is a step of adding an alkali salt and a reducing source to the thallium precipitate and melting it. The order of adding the alkali salt and the reducing source may be any order, but it is preferable that the alkali salt and the reducing source are placed in the same container and then heated and melted in the thallium precipitate.
予め、前記タリウム沈殿物を炉で加温して溶融させるために乾燥することが好ましい。
前記乾燥は、炉を用いて、１５０℃以下の温度で水分を減量させるために行われる。
前記アルカリ塩としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）などが挙げられる。
前記アルカリ塩の添加量としては、前記タリウム沈殿物に対して、０．３ｇ／ｇ以下が好ましく、０．２ｇ／ｇ〜０．３ｇ／ｇがより好ましい。
前記還元源としては、炭素等を含み高温でも使用可能な還元剤であれば特に制限はなく、高温であるため固体の還元源を用いることが好ましく、例えば、コークス、木炭、樹脂などが挙げられる。これらの中でも、コークスが特に好ましい。前記コークスは粉体であってもよい。
前記還元源の添加量としては、前記タリウム沈殿物に対して、０．０２ｇ／ｇ以下が好ましく、０．０１ｇ／ｇ以下がより好ましい。
溶融は、加温によって、アルカリ塩、タリウム殿物、及び還元源が主量の溶融されたアルカリ塩によるアルカリ浴中にて反応が進行し、金属タリウムが回収される。
溶融温度は、７００℃以上が好ましく、７００℃〜１，０００℃がより好ましく、８００℃〜８５０℃が更に好ましい。なお、前記溶融温度の上限は、反応において揮発分とのバランスにより決められる。
溶融時間は、特に制限はなく、目的に応じて適宜選択することができるが、３０分間〜６０分間が好ましい。
It is preferable to dry the thallium precipitate in advance to heat and melt the thallium precipitate.
The drying is performed using a furnace in order to reduce moisture at a temperature of 150 ° C. or lower.
There is no restriction | limiting in particular as said alkali salt, According to the objective, it can select suitably, For example, sodium hydroxide (NaOH), potassium hydroxide (KOH) etc. are mentioned.
As addition amount of the said alkali salt, 0.3 g / g or less is preferable with respect to the said thallium deposit, and 0.2 g / g-0.3 g / g are more preferable.
The reducing source is not particularly limited as long as it is a reducing agent that contains carbon or the like and can be used even at high temperatures. It is preferable to use a solid reducing source because of the high temperature, and examples thereof include coke, charcoal, and resin. . Among these, coke is particularly preferable. The coke may be a powder.
The amount of the reducing source added is preferably 0.02 g / g or less, and more preferably 0.01 g / g or less with respect to the thallium precipitate.
In the melting, the reaction proceeds in an alkali bath with the alkali salt, the thallium deposit, and the alkali salt in which the reduction source is the main amount of the molten salt by heating, and the metal thallium is recovered.
The melting temperature is preferably 700 ° C or higher, more preferably 700 ° C to 1,000 ° C, and still more preferably 800 ° C to 850 ° C. The upper limit of the melting temperature is determined by the balance with volatile components in the reaction.
The melting time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30 minutes to 60 minutes.
前記タリウム沈殿物としては、特に制限はなく、目的に応じて適宜選択することができ、臭化タリウム（ＴｌＢｒ）及び塩化タリウム（ＴｌＣｌ）のいずれを用いても還元溶融は可能である。
これにより、臭素、塩素等のハロゲン元素によるハロゲン化タリウムを原料として溶融還元法により質量品位で９９％以上の高純度の金属タリウムを製造できる。なお、フッ化タリウムについても条件を設定すれば使用できる。
There is no restriction | limiting in particular as said thallium precipitate, According to the objective, it can select suitably, Even if it uses any of thallium bromide (TlBr) and thallium chloride (TlCl), reductive melting is possible.
As a result, high-purity metal thallium having a mass quality of 99% or more can be produced by melt reduction using raw material thallium halide such as bromine and chlorine as a raw material. Note that thallium fluoride can be used if conditions are set.
本発明の金属タリウムの製造方法においては、前記タリウム沈殿物の代わりにハロゲン化タリウムを用い、該ハロゲン化タリウムにアルカリ塩及び還元源を加えて、加温して溶融する態様とすることもできる。前記ハロゲン化タリウムとしては、例えば、臭化タリウム、塩化タリウムなどが挙げられる。 In the method for producing metal thallium according to the present invention, a thallium halide may be used in place of the thallium precipitate, and an alkali salt and a reducing source may be added to the thallium halide, followed by heating and melting. . Examples of the thallium halide include thallium bromide and thallium chloride.
ここで、図２は、本発明の金属タリウムの製造方法の一例を示すタリウム分離及び回収プロセスを示す工程図である。
まず、室温条件下で、鉛電気炉煙灰に水を加え、硫酸を加えて撹拌し、固液分離する（硫酸浸出工程）。前記硫酸浸出工程では、鉛電気炉煙灰に水をスラリー濃度４５０ｇ／Ｌ以下になるように加える。次に、硫酸を加えて室温以上で１時間以上撹拌し、固液分離する。固液分離としては加圧ろ過が好ましい。
Here, FIG. 2 is a process diagram showing a thallium separation and recovery process showing an example of the method for producing metal thallium of the present invention.
First, water is added to lead electric furnace smoke ash under room temperature conditions, sulfuric acid is added and stirred, and solid-liquid separation is performed (sulfuric acid leaching step). In the sulfuric acid leaching step, water is added to the lead electric furnace smoke ash so that the slurry concentration is 450 g / L or less. Next, sulfuric acid is added, and the mixture is stirred for 1 hour or more at room temperature or more, and solid-liquid separation is performed. As solid-liquid separation, pressure filtration is preferred.
次に、硫酸浸出残渣に酸化剤を添加して撹拌し、固液分離する（酸化浸出工程）。前記酸化浸出工程では、硫酸浸出残渣に水をスラリー濃度６００ｇ／Ｌ以下になるように加えて撹拌する。次に、硫酸を添加してｐＨ０．３以下に調整する。酸化剤をタリウムに対して１．５〜３倍当量添加して室温以上で１時間以上撹拌し、固液分離する。固液分離としては加圧ろ過が好ましい。 Next, an oxidizing agent is added to the sulfuric acid leaching residue and stirred, and solid-liquid separation is performed (oxidation leaching step). In the oxidation leaching step, water is added to the sulfuric acid leaching residue so as to have a slurry concentration of 600 g / L or less and stirred. Next, sulfuric acid is added to adjust the pH to 0.3 or less. An oxidizing agent is added in an amount of 1.5 to 3 times the amount of thallium, and the mixture is stirred at room temperature or more for 1 hour or more, and solid-liquid separated. As solid-liquid separation, pressure filtration is preferred.
次に、室温条件下で、酸化浸出液としてのタリウム含有溶液に還元剤を添加して撹拌し、沈殿したタリウム沈殿物を固液分離する（還元工程）。なお、前記タリウム含有溶液には、必要に応じて臭素又は塩素を添加することが好ましい。前記還元工程では、前記タリウム含有溶液に還元剤をタリウムに対して０．３倍当量〜０．５倍当量添加して室温以上で１時間以上撹拌し、固液分離する。固液分離としては加圧ろ過が好ましい。 Next, a reducing agent is added to the thallium-containing solution as the oxidative leachate and stirred under room temperature conditions, and the precipitated thallium precipitate is subjected to solid-liquid separation (reduction step). In addition, it is preferable to add bromine or chlorine to the thallium-containing solution as necessary. In the reduction step, the reducing agent is added to the thallium-containing solution in an amount of 0.3 to 0.5 equivalents with respect to thallium, and stirred at room temperature or higher for 1 hour or longer to perform solid-liquid separation. As solid-liquid separation, pressure filtration is preferred.
次に、乾燥したタリウム沈殿物にアルカリ塩及び還元源を加えて溶融させる（還元溶融工程）。前記還元溶融工程では、乾燥した臭化タリウム（ＴｌＢｒ）に固体ＮａＯＨを０．３ｇ／ｇ−ＴｌＢｒ以下、及びコークス０．０２ｇ／ｇ−ＴｌＢｒ以下を加え、８００℃以上で３０分間以上溶融すると、金属タリウムが得られる。好ましくは、ＮａＯＨ（水酸化ナトリウム）は０．２ｇ／ｇ−ＴｌＢｒ〜０．３ｇ／ｇ−ＴｌＢｒ、コークスは０．０１ｇ／ｇ−ＴｌＢｒ以下加え、８００℃以上で３０分間以上溶融すると、金属タリウムが得られる。
以上により、９９質量％以上の高純度の金属タリウムが得られる。
Next, an alkali salt and a reducing source are added to the dried thallium precipitate and melted (reduction melting step). In the reducing and melting step, 0.3 g / g-TlBr or less of solid NaOH and 0.02 g / g-TlBr or less of coke are added to dried thallium bromide (TlBr) and melted at 800 ° C. or more for 30 minutes or more. Metal thallium is obtained. Preferably, NaOH (sodium hydroxide) is added in an amount of 0.2 g / g-TlBr to 0.3 g / g-TlBr, coke is added in an amount of 0.01 g / g-TlBr or less and molten at 800 ° C. or more for 30 minutes or more. Is obtained.
As a result, 99% by mass or more of high-purity metal thallium is obtained.
本発明の金属タリウムの製造方法によれば、高温の酸性溶液を使用せずに、簡易な方法で、短時間で高純度の金属タリウムを効率よく製造することができる。本発明の金属タリウムの製造方法により製造された高純度の金属タリウムは、例えば、光ファイバー、複写器レンズ、高屈折光学ガラス等の光学分野、特殊ヒューズ、低凝固点温度計、脱酸剤などに幅広く用いられる。 According to the method for producing metal thallium of the present invention, high-purity metal thallium can be efficiently produced in a short time without using a high-temperature acidic solution. The high-purity metal thallium produced by the metal thallium production method of the present invention is widely used in optical fields such as optical fibers, copier lenses, and high refractive optical glasses, special fuses, low freezing point thermometers, deoxidizers, and the like. Used.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
−鉛電気炉煙灰−
実施例で用いた非鉄製錬所にて発生した鉛電気炉煙灰の組成について、下記の表１に示す。なお、Ｂｒ及びＣｌ以外はＩＣＰ法、Ｂｒ及びＣｌはイオンクロマト法で測定した（以下同様に測定した）。
-Lead electric furnace smoke ash-
The composition of the lead electric furnace smoke generated at the non-ferrous smelter used in the examples is shown in Table 1 below. In addition, except for Br and Cl, the ICP method was used, and Br and Cl were measured by an ion chromatography method (hereinafter, the same measurement was performed).
（実施例１）
室温（２５℃）条件下で、５Ｌビーカー内で、前記鉛電気炉煙灰１．６ｋｇに水を加えて４Ｌにし、９５質量％硫酸４６６ｇを加えて３００ｒｐｍで２時間撹拌し、加圧ろ過した（硫酸浸出工程）。なお、撹拌にはバッフル４枚、直径９０ｍｍの２段タービン羽を用いた。
Example 1
Under a room temperature (25 ° C.) condition, water was added to 1.6 kg of the lead electric furnace smoke ash to 4 L in a 5 L beaker, 466 g of 95% by mass sulfuric acid was added, and the mixture was stirred at 300 rpm for 2 hours and filtered under pressure ( Sulfuric acid leaching process). For stirring, four baffles and two-stage turbine blades with a diameter of 90 mm were used.
室温（２５℃）条件下で、５Ｌビーカー内で、硫酸浸出残渣１．３８ｋｇに水を加えて４Ｌにして撹拌し、９５質量％硫酸３５４ｇを添加してｐＨ０．３以下にした。酸化剤として過マンガン酸カリウム４．９ｇを添加して３００ｒｐｍで２時間撹拌し、加圧ろ過した（酸化浸出工程）。なお、撹拌にはバッフル４枚、直径９０ｍｍの２段タービン羽を用いた。 Under a room temperature (25 ° C.) condition, water was added to 1.38 kg of the sulfuric acid leaching residue in a 5 L beaker to make 4 L, and 354 g of 95% by mass sulfuric acid was added to adjust the pH to 0.3 or less. 4.9 g of potassium permanganate was added as an oxidant, stirred at 300 rpm for 2 hours, and filtered under pressure (oxidation leaching step). For stirring, four baffles and two-stage turbine blades with a diameter of 90 mm were used.
室温（２５℃）条件下で、５Ｌビーカー内で、前記酸化浸出液３．５７Ｌに還元剤として亜硫酸ソーダ５．５ｇを添加して２００ｒｐｍで２時間撹拌した。なお、撹拌にはバッフル４枚、直径９０ｍｍの２段タービン羽を用いた。次に、沈殿したＴｌＢｒ沈殿物を加圧ろ過して回収した（還元工程）。ＴｌＢｒ沈殿物は乾量で約１５ｇ得られた。 Under a room temperature (25 ° C.) condition, 5.5 g of sodium sulfite as a reducing agent was added to 3.57 L of the oxidative leachate in a 5 L beaker and stirred at 200 rpm for 2 hours. For stirring, four baffles and two-stage turbine blades with a diameter of 90 mm were used. Next, the precipitated TlBr precipitate was collected by pressure filtration (reduction step). About 15 g of TlBr precipitate was obtained in a dry amount.
次に、１００℃で乾燥したＴｌＢｒ沈殿物１０ｇに固体ＮａＯＨを３ｇ、コークス粉体０．１ｇを加えて２号黒鉛るつぼに入れ、耐火レンガで簡易に蓋をし、加温し、８５０℃で３０分間溶融した（還元溶融工程）。
９９．７質量％の高純度の金属タリウムが得られた。得られた金属タリウムの分析結果を表２に示す。分析値は、すべて質量基準であり、質量％、質量ｐｐｍである。
Next, 3 g of solid NaOH and 0.1 g of coke powder are added to 10 g of TlBr precipitate dried at 100 ° C., put in No. 2 graphite crucible, covered with refractory bricks, heated, and heated at 850 ° C. Melted for 30 minutes (reduction melting step).
99.7% by mass of high-purity metal thallium was obtained. Table 2 shows the analysis results of the obtained metal thallium. All analysis values are based on mass, and are mass% and mass ppm.
（実施例２）
前記鉛電気炉煙灰について、硫酸浸出工程を行わず、そのまま酸化浸出工程を行った。
５Ｌビーカー内で、前記鉛電気炉煙灰１．６ｋｇに水を加えて４Ｌにして撹拌し、９５質量％硫酸２０５ｇを添加してｐＨ０．３以下にした。次に、酸化剤として過マンガン酸カリウム３０ｇを添加して３００ｒｐｍで２時間撹拌し、加圧ろ過した（酸化浸出工程）。なお、撹拌にはバッフル４枚、直径９０ｍｍの２段タービン羽を用いた。実施例２では実施例１の６倍量以上の過マンガン酸カリウムを用いた。
(Example 2)
About the said lead electric furnace smoke ash, the sulfuric acid leaching process was not performed but the oxidation leaching process was performed as it was.
In a 5 L beaker, water was added to 1.6 kg of the lead electric furnace smoke ash to 4 L and stirred, and 205 g of 95% by mass sulfuric acid was added to adjust the pH to 0.3 or less. Next, 30 g of potassium permanganate was added as an oxidant, stirred at 300 rpm for 2 hours, and filtered under pressure (oxidation leaching step). For stirring, four baffles and two-stage turbine blades with a diameter of 90 mm were used. In Example 2, potassium permanganate in an amount 6 times or more that in Example 1 was used.
次に、室温（２５℃）条件下で、５Ｌビーカー内で、酸化浸出液３．５７Ｌに還元剤として亜硫酸ソーダ１１．４ｇを添加して２００ｒｐｍで２時間撹拌した。なお、撹拌にはバッフル４枚、直径９０ｍｍの２段タービン羽を用いた。次に、沈殿したＴｌＢｒ沈殿物を加圧ろ過して回収した（還元工程）。ＴｌＢｒ沈殿物は乾量で約４ｇ得られた。得られた実施例２のＴｌＢｒ沈殿物量は、実施例１の３分の１以下であった。
得られた実施例１及び２のＴｌＢｒ沈殿物の分析結果を表３に示す。なお、得られたタリウム沈殿物にアルカリ塩及び還元源を加えて溶融すれば、金属タリウムが回収できる。
Next, 11.4 g of sodium sulfite as a reducing agent was added to 3.57 L of the oxidized leachate in a 5 L beaker under room temperature (25 ° C.) conditions, and the mixture was stirred at 200 rpm for 2 hours. For stirring, four baffles and two-stage turbine blades with a diameter of 90 mm were used. Next, the precipitated TlBr precipitate was collected by pressure filtration (reduction step). About 4 g of TlBr precipitate was obtained in a dry amount. The amount of TlBr precipitate obtained in Example 2 was not more than one-third that of Example 1.
The analysis results of the obtained TlBr precipitates of Examples 1 and 2 are shown in Table 3. In addition, metal thallium can be recovered by adding an alkali salt and a reducing source to the obtained thallium precipitate and melting it.
（実施例３）
塩化タリウム（ＴｌＣｌ）試薬（和光純薬工業株式会社）１０ｇに固体ＮａＯＨを３ｇ、コークス０．１ｇを加えて２号黒鉛るつぼに入れ、耐火レンガで簡易に蓋をし、加温し、８５０℃で３０分間溶融させた（還元溶融工程）。
９９．５質量％の高純度の金属タリウムが得られた。得られた金属タリウムの分析結果を表４に示す。なお、臭素は、塩化タリウム（ＴｌＣｌ）試薬中に不純分として含まれていたものである。
(Example 3)
Add 3 g of solid NaOH and 0.1 g of coke to 10 g of thallium chloride (TlCl) reagent (Wako Pure Chemical Industries, Ltd.), place it in No. 2 graphite crucible, simply cover with refractory bricks, heat, and heat at 850 ° C For 30 minutes (reduction melting step).
99.5% by mass of high-purity metal thallium was obtained. Table 4 shows the analysis results of the obtained metal thallium. Bromine was contained as an impurity in the thallium chloride (TlCl) reagent.
本発明の金属タリウムの製造方法は、従来のような高温の２００℃の濃硫酸を用いる必要がなく、セメンテーション反応よりも短い時間で高純度の金属タリウムを効率よく製造できるので、光ファイバー、複写器レンズ、高屈折光学ガラス等の光学分野、特殊ヒューズ、低凝固点温度計、脱酸剤などの産業上さまざまな分野で使用される有価金属であるタリウム（Ｔｌ）の製造方法として好適である。 The metal thallium production method of the present invention does not require the use of high-temperature concentrated sulfuric acid at 200 ° C. as in the prior art, and can efficiently produce high-purity metal thallium in a shorter time than the cementation reaction. It is suitable as a method for producing thallium (Tl), which is a valuable metal used in various industrial fields such as optical fields such as instrument lenses and high refractive optical glass, special fuses, low freezing point thermometers, and deoxidizers.
Claims (7)
アルカリ塩がＮａＯＨ及びＫＯＨのいずれかであり、
還元源がコークスである請求項１から２のいずれかに記載の金属タリウムの製造方法。 The thallium precipitate is either thallium bromide or thallium chloride,
The alkali salt is either NaOH or KOH;
The method for producing metal thallium according to claim 1, wherein the reducing source is coke.
前記硫酸残渣に水、硫酸及び酸化剤の少なくともいずれかを加えてスラリーとし、該スラリーを酸化浸出液と残渣とに固液分離する酸化浸出工程と、
を含む請求項１から３のいずれかに記載の金属タリウムの製造方法。 A sulfuric acid leaching step in which at least one of water and sulfuric acid is added to a lead electric furnace smoke ash containing thallium and bromine to form a slurry, and the slurry is solid-liquid separated into a sulfuric acid leachate and a sulfuric acid residue;
Adding at least one of water, sulfuric acid, and an oxidizing agent to the sulfuric acid residue to form a slurry, and oxidizing and leaching the solid to separate the slurry into an oxidative leachate and a residue;
The manufacturing method of the metal thallium in any one of Claim 1 to 3 containing this.
還元源がコークスである請求項５に記載の金属タリウムの製造方法。 The thallium halide is either thallium bromide or thallium chloride,
The method for producing metal thallium according to claim 5, wherein the reducing source is coke.
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| JP2015183213A (en) * | 2014-03-24 | 2015-10-22 | Ｄｏｗａホールディングス株式会社 | Method for producing metal thallium |
| CN113502404A (en) * | 2021-06-11 | 2021-10-15 | 清华大学 | Method for recovering thallium from flue gas and device for implementing method |
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| JPS60122722A (en) * | 1983-12-02 | 1985-07-01 | Mitsui Mining & Smelting Co Ltd | Manufacture of various kinds of thallium compounds from liquid containing thallium |
| JPH10251772A (en) * | 1997-03-13 | 1998-09-22 | Mitsubishi Materials Corp | Production of high purity thallium metal |
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| JPS60122722A (en) * | 1983-12-02 | 1985-07-01 | Mitsui Mining & Smelting Co Ltd | Manufacture of various kinds of thallium compounds from liquid containing thallium |
| JPH10251772A (en) * | 1997-03-13 | 1998-09-22 | Mitsubishi Materials Corp | Production of high purity thallium metal |
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| JP2015183213A (en) * | 2014-03-24 | 2015-10-22 | Ｄｏｗａホールディングス株式会社 | Method for producing metal thallium |
| CN113502404A (en) * | 2021-06-11 | 2021-10-15 | 清华大学 | Method for recovering thallium from flue gas and device for implementing method |
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